U.S. patent number 9,180,327 [Application Number 14/239,155] was granted by the patent office on 2015-11-10 for compositions and methods for remediation of chlorinated polyaromatic compounds.
This patent grant is currently assigned to NBIP, LLC. The grantee listed for this patent is Burt R. Sookram, John W. Veenstra. Invention is credited to Burt R. Sookram, John W. Veenstra.
United States Patent |
9,180,327 |
Sookram , et al. |
November 10, 2015 |
Compositions and methods for remediation of chlorinated
polyaromatic compounds
Abstract
The present invention relates to compositions and methods that
are effective in the remediation of contaminants found in natural
sources such as groundwater, surface water, soil and manufactured
products. The disclosed compositions and methods provide a method
for remediating chlorinated polyaromatic compounds by treating them
under pressure and heat with concentrated acids and chloride salts.
After decomposition has occurred, the resulting acid that is
produced is made dermal and non-corrosive. The compositions and
methods claimed herein make the product safe to be in contact with
humans and animal tissue without causing injury.
Inventors: |
Sookram; Burt R. (Palm Harbor,
FL), Veenstra; John W. (Plano, TX) |
Applicant: |
Name |
City |
State |
Country |
Type |
Sookram; Burt R.
Veenstra; John W. |
Palm Harbor
Plano |
FL
TX |
US
US |
|
|
Assignee: |
NBIP, LLC (Plano, TX)
|
Family
ID: |
47715505 |
Appl.
No.: |
14/239,155 |
Filed: |
August 17, 2012 |
PCT
Filed: |
August 17, 2012 |
PCT No.: |
PCT/US2012/051402 |
371(c)(1),(2),(4) Date: |
March 03, 2014 |
PCT
Pub. No.: |
WO2013/026014 |
PCT
Pub. Date: |
February 21, 2013 |
Prior Publication Data
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|
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Document
Identifier |
Publication Date |
|
US 20140206921 A1 |
Jul 24, 2014 |
|
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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61524561 |
Aug 17, 2011 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C02F
1/76 (20130101); A62D 3/20 (20130101); C02F
2101/363 (20130101) |
Current International
Class: |
A62D
3/36 (20070101); A62D 3/20 (20070101); C02F
1/76 (20060101) |
Field of
Search: |
;588/312,318,313,406,405 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
International Search Report mailed Jan. 9, 2013; Authorized
Officer: Lee W. Young. cited by applicant.
|
Primary Examiner: Johnson; Edward
Attorney, Agent or Firm: Winstead PC
Parent Case Text
CROSS-REFERENCES TO RELATED APPLICATIONS
This Application claims the benefit under 35 U.S.C. .sctn.119(e) of
U.S. Provisional Patent Application Ser. No. 61/524,561 filed Aug.
17, 2011, which is incorporated herein by reference in its entirety
as if fully set forth herein.
Claims
What is claimed is:
1. A composition that is effective in the remediation of
chlorinated polyaromatic compounds, said composition comprising a
mixture of hydrochloric acid, chloride salt and water, wherein said
composition has a pH of less than 2.0 when the mixture is present
at a concentration of 0.1% by weight and a proton count ranging
from 2.0.times.10.sup.24 to 4.5.times.10.sup.24 when the mixture is
present at a concentration of 1% by weight.
2. The composition of claim 1, wherein the chlorinated polyaromatic
compound is a polychlorinated biphenyl.
3. The composition of claim 1, wherein the chloride salt is
selected from ammonium chloride, sodium chloride, potassium
chloride, calcium chloride, magnesium chloride, aluminum chloride,
zinc chloride, nickel chloride, lead chloride, ferrous chloride,
ferric chloride, gold chloride and combinations or mixtures
thereof.
4. A method for the remediation of chlorinated polyaromatic
compounds comprising the steps of: a) mixing concentrated
hydrochloric acid with water to cause an exothermic reaction; b)
mixing an amount of a composition comprising at least one
chlorinated polyaromatic compound to the mixture of hydrochloric
acid and water in step a); c) subjecting the chlorinated
polyaromatic compound and acid mixture of step b) to increased
pressure, thereby increasing the temperature of the mixture to at
least 600.degree. C.; d) maintaining the temperature of the mixture
of step c) at or above 600.degree. C. for at least 120 seconds; and
e) adding a chloride salt to the chlorinated polyaromatic compound
and acid mixture of step d).
5. The method of claim 4, wherein the initial mixture of
hydrochloric acid and water is maintained at a temperature of at
least 60.degree. C.
6. The method of claim 4, wherein the temperature of the initial
mixture of hydrochloric acid and water ranges from 60.degree. C. to
65.degree. C.
7. The method of claim 4, wherein the chlorinated polyaromatic
compound and acid mixture is maintained at a temperature of at
least 600.degree. C. for at least 60 seconds.
8. The method of claim 4, wherein the chlorinated polyaromatic
compound and acid mixture is maintained at a temperature of at
least 600.degree. C. for at least 120 seconds.
9. The method of claim 4, wherein the chlorinated polyaromatic
compound and acid mixture is maintained at a temperature of at
least 650.degree. C. for 60 seconds to 120 seconds.
10. The method of claim 4, wherein the temperature of the
chlorinated polyaromatic compound and acid mixture is increased
from a starting temperature of at least 60.degree. C. to at least
600.degree. C.
11. The method of claim 10, wherein the temperature of the
chlorinated polyaromatic compound and acid mixture is increased by
subjecting the mixture to increased pressure.
12. The method of claim 11, wherein the pressure of the chlorinated
polyaromatic compound and acid mixture is increased from
atmospheric pressure to a pressure ranging from 980 kPA to 1150
kPA.
13. The method of claim 4, wherein the chloride salt is added to
the chlorinated polyaromatic compound and acid mixture at a
concentration of 5% to 30% by weight of the hydrochloric acid.
14. The method of claim 4 wherein, the chloride salt is selected
from ammonium chloride, sodium chloride, potassium chloride,
calcium chloride, magnesium chloride, aluminum chloride, zinc
chloride, nickel chloride, lead chloride, ferrous chloride, ferric
chloride, gold chloride and combinations or mixtures thereof.
15. The method of claim 4, wherein the composition comprising at
least one chlorinated polyaromatic compound is added to the mixture
of hydrochloric acid and water at a concentration of 35 parts to
150 parts of the composition to 1 part of hydrochloric acid and
water.
16. The method of claim 15, wherein the ratio of chlorinated
polyaromatic compound to acid ranges from 50-125:1.
17. The method of claim 15, wherein the ratio of chlorinated
polyaromatic compound to acid ranges from 75-100:1.
Description
FIELD OF THE INVENTION
The present invention relates to compositions and methods that are
effective in the remediation of contaminants found in natural
sources such as groundwater, surface water, soil and manufactured
products.
BACKGROUND OF THE INVENTION
PCBs are organic compounds composed of two benzene rings that are
joined and containing at least 1 to 10 chlorine atoms. There can be
209 theoretically different combination of PCBs, of which 130 are
found commercially.
PCBs are a group of chlorinated polyaromatic compounds including
chlorinated polycyclic aromatic hydrocarbons that became widely
used in numerous commercial applications starting in the early
1930s because of their unique thermal stability and non-reactive
nature. It has recently been discovered that PCBs are also highly
toxic. Because of this toxicity, the manufacture and use of PCBs
has been greatly curtailed and their use has generally been limited
to closed systems. However, because of their thermal and chemical
stability and non-reactive nature, PCBs exist in significant
amounts in the environment and have found their way into all levels
of the food chain. There is therefore a need for an efficient and
economic method for removing PCBs and other polyaromatic compounds
from the environment.
Some basic PCB properties are: 1) it is odorless, tasteless, clear
to pale yellow viscous liquid but when the chlorination is higher,
the viscosity increases and the color becomes deeper yellow; 2) in
water, it has a very low solubility, which increases with organic
solvents and fats. The flash point temperature is between 170 to
380.degree. C.; 3) it is resistant to oxidation, reduction,
addition, elimination and electronic substitution reactions; 4) as
the percentage of chlorine increases, the melting point and
lipophilicity, which is the ability to dissolve in fats, also
increases but at the same time its water solubility rate decreases;
5) PCBs can very easily penetrate skin, PVC and latex but is
impermeable to butyl rubber, nitrile rubber, neoprene, and
polyvinyl acetate; 6) it is very stable and does not decompose very
easily and; 7) chemical, thermal and biochemical reactions are
difficult because it generates very toxic products such as
dibenzoidoxin and dibenzofurans with oxidation.
PCBs have been used in several applications such as: Coolants in
insulation fluids for transformers, in fluorescent and electrical
transformers, paints, cements, pesticides, protective covers in
electrical wiring, caulking sealants, adhesives, waterproofing
compounds, flame retardant products, several heavy industrial oils,
electric fluids in transformers, capacitors, de-dusting agents,
cutting oils, heat transfer fluids, hydraulic lubricants, asphalt
roofing materials, carbonless copy paper, surgical implants,
compressor oil, dielectric fluid, dyes, electromagnets, grout,
inks, mixed with asbestos, natural gas pipelines, pesticides,
plasticizers, rubberizes, space heaters, submersible well pumps,
tar paper and wax extenders. PCBs have also been known to be by
products of cigarette smoke.
PCBs can stay in the body for long periods after being absorbed by
the fat cells, and also can be transmitted to the newborns through
breast feeding. The ill effects of PCBs have been observed in liver
damage, dental decay, rashes, irregular menstrual cycles,
still-born fetuses, unusual skin sores and cancer.
Exposure to PCBs can also cause cancer, heart disease, reproductive
problems, reduced sperm count, birth defects, immune suppression
and endocrine disruption. For pregnant women, there is a special
risk of defects in unborn and newborn child. These defects can
include but are not limited to, lower birth rates, smaller head
circumference, premature birth, depressed responsiveness, impaired
visual recognition, poor short term memory, weight gain deficits,
reduced IQ and/or difficulty paying attention.
Reports on the occurrence of PCBs in fish, mussels, seals, sea
birds and birds of prey first appeared in 1966. In 1967, PCBs were
detected in human adipose tissue, albeit in low concentrations. In
1968, PCBs from a leaking cooling system contaminated a rice oil
tank at a food factory in Japan. As a result of the consumption of
the contaminated rice oil, 1,000 people fell ill with a disease
subsequently known worldwide as Yusho Disease.
Some of the methods by which PCBs can be decomposed include: 1)
Incineration at a temperature of 1200.degree. C. with excess oxygen
and fuel; 2) Ultrasound where water undergoes thermolysis oxidation
of the PCBs reducing it to Carbon Dioxide, Carbon Monoxide and
hydrocarbons (CH.sup.+) and releasing the Chlorine (Cl.sup.-); 3)
Irradiation wherein the PCBs are mixed with mineral oil or
isopropyl alcohol with potassium hydroxide and then bombarded with
gamma rays, releasing the Chlorine from the biphenyl; 4) Pyrolysis
which uses a plasma arc process to achieve the 1200.degree. C. but
with an inert environment; 5) Use of microbes to attack the Carbon
element in the PCBs; 6) Use of Enzymes as a catalyst to speed up
the decomposition of the PCBs and 7) Chemical substitution to
replace the Chlorine with polyethylene glycol, which must be done
under nitrogen to accommodate the proper reaction which yields an
insoluble aryl polyglycol that is filtered out. However, these
methods are expensive and difficult to perform on a large
scale.
Conventionally, PCBs were disposed of solely by incineration.
However, this method is very likely to produce harmful materials
(e.g., dioxins) such as by-products and, therefore, incineration
disposal is not employed at present. Thus, there is a need to
develop a process for decomposing PCBs that is not expensive and
does not produce any harmful byproducts. In an attempt to find a
process that produces no harmful materials (e.g., dioxins), there
has recently been proposed a process wherein PCBs are oxidatively
decomposed in supercritical water having a temperature of
374.degree. C. or above and containing an oxidizing agent. However,
since PCBs are chemically stable, it would be preferable to
decompose PCBs at a temperature of 600.degree. C. or higher.
SUMMARY OF THE INVENTION
The disclosed compositions and methods provide a method for
remediating polychlorinated biphenyls by treating them under
pressure and heat. After decomposition has occurred, the resulting
composition that is produced is made dermal and non-corrosive. The
compositions and methods claimed herein make the product safe to be
in contact with humans and animal tissue without causing
injury.
An embodiment of the invention is directed to a composition that is
effective in the remediation of chlorinated polyaromatic compounds,
said composition comprising a mixture of hydrochloric acid,
chloride salt and water, wherein said mixture has a pH of less than
2.0 at a concentration of 0.1% by weight and a proton count ranging
from 2.0.times.10.sup.24 to 4.5.times.10.sup.24 at a concentration
of 1% by weight.
A further embodiment of the invention is directed to a method for
the remediation of chlorinated polyaromatic compounds comprising
the steps of mixing concentrated hydrochloric acid with water to
cause an exothermic reaction; mixing an amount of a composition
comprising at least one chlorinated polyaromatic compound with the
mixture of hydrochloric acid and water; subjecting the chlorinated
polyaromatic compound and acid mixture to increased pressure, and
increasing the temperature of the mixture to at least 600.degree.
C.; maintaining the temperature of the mixture at or above
600.degree. C. for at least 120 seconds; and adding a chloride salt
to the chlorinated polyaromatic compound and acid mixture.
DESCRIPTION OF EXEMPLARY EMBODIMENTS
In this instant specification and in the claims that follow,
reference will be made to a number of terms that shall be defined
to have the following meanings:
Throughout this specification, unless the context requires
otherwise, the word "comprise," or variations such as "comprises"
or "comprising," will be understood to imply the inclusion of a
stated step or group of steps but not the exclusion of any other
step or group of steps.
It must be noted that, as used in the specification and the
appended claims, the singular forms "a," "an" and "the" include
plural references unless the context clearly dictates
otherwise.
"Optional" or "optionally" means that the subsequently described
event or circumstance may or may not occur, and that the
description includes instances where the event or circumstance
occurs and instances where it does not.
Ranges may be expressed herein as from "about" one particular
value, and/or to "about" another particular value. When such a
range is expressed, another aspect includes from the one particular
value and/or to the other particular value. Similarly, when values
are expressed as approximations by use of the antecedent "about,"
it will be understood that the particular value forms another
aspect. It will be further understood that the endpoints of each of
the ranges are significant both in relation to the other endpoint
and independently of the other endpoint.
A weight percent of a component, unless specifically stated to the
contrary, is based on the total weight of the formulation or
composition in which the component is included.
"Dermal" is used herein to represent when a product is in contact
with living tissue there is no physical or chemical changes that
occur to the tissue. There is a lack of burning sensation or damage
to such tissue.
The Globally Harmonized System of Classification and Labeling of
Chemicals (GHS) defines skin irritation as "the production of
reversible damage to the skin following the application of a test
substance for up to 4 hours" and defines skin corrosion as "the
production of irreversible damage to the skin; namely, visible
necrosis through the epidermis and into the dermis, following the
application of a test substance for up to 4 hours."
An embodiment of the invention is directed to a composition that is
effective in the remediation of chlorinated polyaromatic compounds,
said composition comprising a mixture of hydrochloric acid,
ammonium chloride and water.
In a further embodiment of the invention, the chlorinated
polyaromatic compound that is effectively remediated is a
polychlorinated biphenyl or PCB.
An embodiment of the invention is directed to a highly protonated
composition that is effective in the remediation of chlorinated
polyaromatic compounds, said composition having a low pH and
non-corrosive properties, and having a proton count between
2.0.times.10.sup.24 to 4.5.times.10.sup.24, when present at a
concentration of 1% by weight and a pH of less than 2 when present
at a concentration of 0.1% by weight.
In certain embodiments of the invention, the pH of the composition
of the invention ranges from 1.55 to 1.65, when present at a
concentration of 0.1% by weight.
In other embodiments of the invention, a solution comprising 0.1%
by weight of the mixture of hydrochloric acid, ammonium chloride
and water is used to remediate chlorinated polyaromatic compounds
that are present in a solution or a surface. In additional
embodiments of the invention, the solution comprising 0.1% by
weight of the mixture of hydrochloric acid, ammonium chloride and
water has a pH of less than 2.0. A composition comprising 1% by
weight of the mixture of hydrochloric acid, ammonium chloride and
water has a proton count ranging from 2.0.times.10.sup.24 to
4.5.times.10.sup.24, and color properties that will vary by the
color of the original contamination.
In an embodiment of the invention, a composition comprising 1% by
weight of the mixture of hydrochloric acid, ammonium chloride and
water has a proton count ranging from 3.0.times.10.sup.24 to
3.9.times.10.sup.24. In other embodiments of the invention, the
composition comprising 1% by weight of the mixture of hydrochloric
acid, ammonium chloride and water has a proton count of at least
3.15.times.10.sup.24.
An embodiment of the invention is directed to a method for the
remediation of chlorinated polyaromatic compounds comprising the
steps of mixing concentrated hydrochloric acid with water to cause
an exothermic reaction, mixing an amount of a composition
comprising at least one chlorinated polyaromatic compound to the
mixture of hydrochloric acid and water, subjecting the chlorinated
polyaromatic compound and acid mixture to increased pressure,
thereby increasing the temperature of the mixture to at least
600.degree. C., maintaining the temperature of the mixture at or
above 600.degree. C. for at least 120 seconds and adding a chloride
salt to the chlorinated polyaromatic compound and acid mixture.
In certain embodiments of the invention, the initial mixture of
hydrochloric acid and water is maintained at a temperature of at
least 60.degree. C. In an embodiment of the invention, the
temperature of the initial mixture of hydrochloric acid and water
ranges from 60.degree. C. to 65.degree. C.
In certain embodiments of the invention, the chlorinated
polyaromatic compound and acid mixture is maintained at a
temperature of at least 600.degree. C. for at least 60 seconds. In
other embodiments of the invention, the chlorinated polyaromatic
compound and acid mixture is maintained at a temperature of at
least 600.degree. C. for at least 120 seconds. In other embodiments
of the invention, the chlorinated polyaromatic compound and acid
mixture is maintained at a temperature of at least 650.degree. C.
for 60 seconds to 120 seconds.
According to an embodiment of the invention, the temperature of the
chlorinated polyaromatic compound and acid mixture is increased
from a starting temperature of at least 60.degree. C. to at least
600.degree. C. In certain embodiments of the invention, the
temperature is increased by subjecting the chlorinated polyaromatic
compound and acid mixture to increased pressure. In certain
embodiments of the invention, the pressure of the chlorinated
polyaromatic compound and acid mixture is increased from
atmospheric pressure to at least 1013 kPA. In other embodiments of
the invention, the pressure of the chlorinated polyaromatic
compound and acid mixture is increased from atmospheric pressure to
at least 1057 kPA.
In certain embodiments of the invention the pressure is increased
from atmospheric pressure to between 980 kPA to 1150 kPA.
In accordance with certain embodiments of the invention, the
chloride salt is added to the chlorinated polyaromatic compound and
acid mixture at a concentration of 5% to 30% by weight of the
hydrochloric acid that is initially used.
In certain embodiments of the invention, the chloride salt is
selected from ammonium chloride, sodium chloride, potassium
chloride, calcium chloride, magnesium chloride, aluminum chloride,
zinc chloride, nickel chloride, lead chloride, ferrous chloride,
ferric chloride, gold chloride and combinations or mixtures
thereof.
In accordance with certain embodiments of the invention, the
composition comprising at least one chlorinated polyaromatic
compound is added to the mixture of hydrochloric acid and water at
a concentration of 35 parts to 150 parts of the composition to 1
part of hydrochloric acid and water. In other embodiments of the
invention the ratio of chlorinated polyaromatic compound to acid
ranges from 50-125:1 to 75-100:1.
WORKING EXAMPLES
Example 1
A 2 gallon glass-lined pressure reactor is used, to which is added
40 grams of a 50% concentrated hydrochloric acid followed by 10
grams of distilled water. The reaction is exothermic. The
temperature recorded for a single experiment was 60.degree. C.
5,000 grams of PCBs was added and the temperature was recorded. The
pressure was gradually raised from 101.32 kPA (normal atmospheric
pressure), which resulted in an increase in the temperature of the
mixture. The pressure was increased to 1013 kPA or until a
temperature of 600.degree. C. was reached. Once this was achieved,
it was held steady for 120 seconds and the pressure was released. A
previously dissolved mixture of ammonium chloride and water (6.76
grams and 3.24 grams respectively) was then added to the container.
The resulting composition had a pH of 1.7 and a proton count of
3.6.times.10.sup.24.
Example 2
In the same system as above, 60 grams of a 50% hydrochloric acid
and 10 grams of distilled water was added in the same procedure as
above. Next, 5,000 grams of PCB was metered into the glass lined
reactor. The pressure was increased to 1057 kPA or until the
temperature reached 650.degree. C., the pressure was maintained to
insure a temperature of above 650.degree. C. for 120 seconds. The
pressure was then released and ammonium chloride/water mixture
(10.14 grams/4.86 grams) was then added to the above container. The
resulting composition had a pH of 1.65 and a proton count of
3.25.times.10.sup.24.
After each experimental, a crude dermal test was completed as set
forth below. This consisted of adding a few drops of test liquid on
to a paper towel or lens paper and observing for physical change on
the paper.
The results of the dermal test showed that the product resulting
from the addition of the ammonium chloride/water mixture was not
corrosive, i.e., the product was dermal-friendly.
Determination of Dermal Nature of a Product
Measurement of the dermal nature of a product is done by performing
an absorption application of any acid-salt or base-salt mixture
product using a Pyrex glass stirring rod of at least 250 mm to
apply on a cellulose based material.
A glass stirring rod is inserted into the product to be tested.
Using glass rod, stir the sample to be tested. The glass rod is
rolled on lens cleaning paper. The lens cleaning paper is observed
to determine if there is any corrosion or burning of the paper.
Burning or corrosion of the paper indicates that the product is not
dermal. On the other hand, when there is no noticeable damage to
the test lens paper, the result indicates that the product is
dermal-friendly.
It should be understood that the preceding is merely a description
of one or more embodiments of this invention and that numerous
changes to the disclosed embodiments can be made in accordance with
the disclosure herein without departing from the spirit and scope
of the invention. The preceding description, therefore, is not
meant to limit the scope of the invention.
* * * * *